Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior

ABSTRACT

A process for endowing a polymeric article with a surface layer of an ion-conducting polymer to yield electrical surface resistivity sufficiently low for electrostatic discharge applications is provided. The polymeric article contains one or more immobilized, polymeric components having amine functional groups. The presence of the ion-conducting polymer in the surface layer lowers the surface electrical resistivity into the range suitable for electrostatic discharge applications, between about 1×10 5  and about 1×10 12 Ω/□. Plastic electrostatic dissipation materials produced by the inventive process may find use in the optical, electronics, automotive, entertainment, sporting goods, and medical sectors.

FIELD OF THE INVENTION

The present invention relates, in general to polymers and morespecifically, to a process for incorporating a surface layer of anion-conducting polymer into a polymeric matrix to lower the surfaceresistivity of the material sufficiently to achieve electrostaticdissipation (anti-static behavior).

BACKGROUND OF THE INVENTION

Due to their processability and useful mechanical properties,thermoplastic polymers have found widespread commercial success inconsumer goods, military applications, packaging materials,construction, automobiles, and electronics. However, the vast majorityof plastics are electrical insulators, which can present problems withstatic (triboelectric) charge build-up. Electric charge that builds up,triboelectrically or otherwise, on the surface of an insulating plasticmay not easily move across the surface of the article to recombine.Applications where static build-up on plastics can be problematicinclude aircraft, electronics, and military fabrics/devices. Polymerswith electrostatic dissipation properties are used in a wide variety ofapplications, notably for the prevention of explosions due to chargebuild up in engines and turbines (e.g., U.S. Published PatentApplication No. 2008/0237527 and U.S. Pat. No. 7,527,042) and for theprotection of electronics (e.g., U.S. Pat. Nos. 5,916,486, 5,997,773,and 6,015,509, and U.S. Pat. Nos. 6,687,097; 6,344,412; 6,534,422; and6,459,043).

Electronics can be damaged by static discharge, and combustible orenergetic materials can be ignited or detonated, respectively. Inconsumer applications, plastic electrostatic dissipation materials canbe useful in flooring (e.g. tiles or carpet) and automobile seat covers,which can otherwise build up a static charge due to friction againstshoes or clothing. If electrical insulators are used, these materialscan deliver unwanted “shocks” to the consumer, especially under dryatmospheric conditions. Although conducting polymers that make excellentelectrostatic dissipation materials are now commercially available,their cost per kg is prohibitively higher than commodity plastics, theirprocessability in common plastics processing equipment is poor, andtheir mechanical properties are not well-suited to many applications.Therefore, traditional commodity plastics are usually blended withanti-static agents or conducting fillers to achieve electrostaticdissipation properties.

Materials hereinafter referred to as having “electrostatic dissipationcharacteristics” have surface resistivity in the range of 1×10⁵ to1×10¹²Ω/□ (or volume resistivity in the range of 1×10⁴ to 1×10¹¹ Ω-cm).Many unmodified plastic resins have surface resistivity in the range of1×10¹⁴ to 1×10¹⁵Ω/□, meaning they are electrical insulators. To lowerthe surface resistivity into the electrostatic dissipation range, avariety of processing strategies have been described.

U.S. Published Patent Application No. 2009/0186254 provides anacid-cured resole with no additional additives that possesses low enoughresistivity for electrostatic dissipation applications. The synthesis ofa poly(urea-urethane) based on poly(dimethylsiloxane), which exhibitssufficient conductivity at high humidity for electrostatic dissipationapplications, is disclosed in U.S. Pat. No. 6,841,646.

Inclusion of moieties capable of conduction within the polymer backbonecan also be a successful strategy for electrostatic dissipationmaterials. U.S. Pat. No. 6,586,041 describes a method for achievingelectrostatic dissipation in a transparent polymer material, made fromconductive polymer, crosslinkable polymer, and crosslinking agent, foruse as a thin film for packaging materials. U.S. Pat. No. 7,041,374details the use of metallocene moieties within a polymer backbone toconfer electrostatic dissipation properties.

In another class of electrostatic dissipation polymers, a chemicaladditive can be either applied to the surface or incorporated beneaththe surface of the article. It is common to introduce anti-static agentsduring processing, which are often amphiphilic surfactant molecules. Theanti-static agent typically has an ionic “head” group and a long,non-polar “tail” group. Due to poor thermodynamics of mixing between theionic head group and the plastic, the anti-static agent migrates to thesurface after processing, forming a highly polar layer at the surface.Due to adsorption of atmospheric moisture onto the surface, the surfaceresistivity is significantly lowered.

The anti-static agent may be partially lost due to wear or friction onthe surface during normal use of the plastic article, but theanti-static agent is self-replenishing to some extent because additionalanti-static agent is able to diffuse to the surface over time. Whiletraditional anti-static agents may be useful for common consumerarticles, for demanding applications such as outdoor use, theanti-static agents can be lost due to weathering and/or mechanicalabrasion. Therefore, approaches involving an immobilized anti-staticagent are preferable. For example, U.S. Pat. No. 5,571,472 provides forachieving electrostatic dissipation properties in a shaped resin withoutdamaging physical properties or causing discoloration, via addition of anitrogen-containing compound during molding, followed with coronadischarge treatment to the surface of the shaped article.

Fillers, such as metal particles or carbon fibers, can also be added toa polymer article in order to achieve sufficient conductivity forelectrostatic dissipation. Carbon black has been demonstrated for thispurpose, as have carbon nanotubes and metal nanocomposites. U.S.Published Patent Application No. 2009/0236132 discusses electrostaticdissipation materials comprised of a dispersion of non-insulatingparticles, such as gold or carbon black, and an inherently dissipativepolymer within a thermosetting resin. U.S. Published Patent ApplicationNo. 2009/0281227 discloses a polymer composition consisting of apoly(aryl ether ketone), a poly(biphenyl ether sulfone), and a fibrouscarbon nanofiller that possess electrostatic dissipation properties.

U.S. Pat. No. 7,236,396 and U.S. Published Patent Application No.2004/0126521 describe a high temperature, high strength polymer whichuses a metal oxide to achieve electrostatic dissipation for read/writeheads in magnetic media. Additionally, these references describe theability of the material to be dyed via a pigment while maintaining theirconductive properties.

U.S. Pat. No. 7,476,339 details the use of non-carbonaceous fillers,such as metal oxide particles, within thermoplastic polymers, forelectrostatic dissipation properties. U.S. Published Patent ApplicationNo. 2005/0194572 discusses the polymerization of a thermoplastic in thepresence of a lithium salt, resulting in electrostatic dissipationcapability.

Graphite-filled polymer composites for electrostatic dissipationapplications are described in U.S. Pat. No. 6,746,626. US PublishedPatent Application No. 20060047052 and U.S. Pat. No. 7,897,248 disclosea method for orienting nanotubes within a polymer matrix, leading to anelectrostatic dissipation-capable material. A degradable polymer can beused, along with metal flakes, fibers or powders, to achieveelectrostatic dissipation properties in a moldable article, as describedin U.S. Pat. No. 5,904,980.

Ion-conducting polymers potentially represent another means of loweringthe resistivity of a polymeric article. Of particular relevance to thepresent disclosure are polyamine hydrohalides, a type of ion-conductingpolymer. Electrical properties ofpoly(2-dimethylaminoethylmethacerylate) and its hydrochloride salt, anion-conducting polymer, have been recently reported (Chema J R, MaullickM, Dutta A, Dass N N. Materials Science and Engineering B-Solid StateMaterials for Advanced Technology 2004; 107(2):134-138.). The electricalconductivity of the ion-conducting polymer was found to be in the rangeof 10⁻² to 10⁻⁴ S cm⁻¹. Incorporation of an ion-conducting polymer intoa polymeric matrix is therefore another approach to lowering theelectrical resistivity of the material.

Also relevant to the present disclosure is the infusion processing ofplastic materials. The optical, mechanical, and electrical properties ofvarious plastics may be enhanced by infusion of compounds, functionaladditives, or monomers from solution. Infusion of coloring agents andfunctional additives into polymeric matrices and to articles comprisingsuch matrices has been disclosed in U.S. Pat. Nos. 6,749,646; 6,929,666;7,094,263; 6,733,543: 6,949,127; 6,994,735; and 7,175,675.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a process of incorporatingan ion-conducting polymer into the surface layer of a polymeric article.The ion-conducting polymers of interest are polyamine hydrohalides.Initially, the polymeric article is understood to contain both a hostpolymer and a polyamine component, which may be present as a co-monomer,an immiscible blend component, or an interpenetrating network orsemi-interpenetrating network. The process includes bringing at least apart of the surface of the article in contact with a solvent mixturecontaining:

-   (a) water,-   (b) a carrier conforming to    R₁-[—O—(CH₂)_(n)]_(m)OR₂    -   where R₁ and R₂ independently denote a radical selected from the        group consisting of linear and branched C₁₋₁₈ alkyl, benzyl,        benzoyl, phenyl and H, n is 2 or 3, and m is 1-35,-   (c) an acid H⁺X⁻, where X⁻ represents a halide anion (F⁻, Cl⁻, Br⁻,    or I⁻)-   (d) an optional surface leveling agent, such as diethylene glycol    for a time and at temperature sufficient to infuse at least some of    the solvents and the acid H⁺X⁻ into said article to obtain an    article having a treated surface layer containing a polyamine    hydrohalide, a type of ion-conducting polymer.

The presence of the ion-conducting polymer lowers the surfaceresistivity into the range of between 1×10⁵ and 1×10¹²Ω/□. Plasticelectrostatic dissipation materials produced by the inventive processmay find use in the optical, electronics, automotive, entertainment,sporting goods, and medical sectors.

These and other advantages and benefits of the present invention will beapparent from the Detailed Description of the Invention herein below.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described for purposes of illustrationand not limitation. Except in the operating examples, or where otherwiseindicated, all numbers expressing quantities, percentages, and so forthin the specification are to be understood as being modified in allinstances by the term “about.”

The present invention provides a process involving contacting at least apart of a surface of a polymeric article with a solvent mixture for atime and at a temperature sufficient to infuse at least a portion of thesolvent mixture into the article, the solvent mixture containing (a)water, (b) a carrier conforming to

R₁-[O—(CH₂)_(n)]_(m)OR₂ wherein R₁ and R₂ independently denote a radicalselected from the group consisting of linear and branched C₁₋₁₈ alkyl,benzyl, benzoyl, phenyl and H, wherein n is 2 or 3, and m is 1-35, and(c) an acid H⁺X⁻, wherein X⁻ represents a halide anion selected from thegroup consisting of F⁻, Cl⁻, Br⁻, or I⁻, optionally, (d) a surfaceleveling agent, wherein the polymeric article comprises a host polymerand an immobilized mass fraction of an amine functional species, whereinthe resulting article has a treated surface layer containing a polyaminehydrohalide and a surface resistivity between about 1×10⁵Ω/□ and about1×10¹²Ω/□.

The present invention further provides a process for producing anelectrostatic discharge material by incorporating a surface layer of anion-conducting polymer into a polymeric matrix to lower the surfaceresistivity of the material sufficiently to achieve electrostaticallydissipation (anti-static behavior). Processing is accomplished viainfusion of a strong acid such as hydrogen chloride (HCl) into thesurface of a polymeric article that contains immobilized aminefunctional groups, by immersion of the article in a ternary mixture ofsolvents containing the acid. The amine groups may be present either asa co-monomer in the matrix, or as an interpenetrating network orsemi-interpenetrating network within the topmost 10 to 500 μm of thesurface. The processed article is found to have surface resistivitybetween 1×10⁵ and 1×10¹²Ω/□, sufficient for electrostatic dissipationapplications.

The term “article” as used hereinbelow is understood to refer to anarticle of manufacture, or a semi-finished article in the form pellets,sheet or rod, that are made of polymeric resin or a resinouscomposition. The term “surface layer” as used in the context of thepresent invention refers to an infused layer extending up to 500 μmbeneath the original surface of the host polymer article.

The polymeric materials suitable in the inventive process may bethermoplastic or thermosetting polymers or compositions containing suchpolymers, hereinafter referred to as “host polymers”, which contain anamine-functional co-monomer, or are blended with one of variousamine-functional polymeric components. Among the suitable host polymermaterials are systems containing at least one of (co)polyesters,aliphatic polycarbonate, polyester-polycarbonate copolymers, styreniccopolymers such as styrene-acrylonitrile andacrylonitrile-butadiene-styrene, acrylic polymers such aspolymethylmethacrylate and butylacrylate/styrene-acrylonitrile resins,polyamide, polyurethanes and blends of one or more of these resins.Particularly preferably, the inventive process is applicable tothermoplastic polyurethanes.

The amine functional monomer may be incorporated into the host polymeras a co-monomer, to produce copolymers of random, alternating, or blockymicrostructure. Alternatively, a polyamine may be blended with thesubstrate polymer during processing to form an immiscible or partlymiscible blend. Alternatively, a polyamine may be introduced as aninterpenetrating network or semi-interpenetrating network, by swellingof the host polymer in an amine-functional monomer and initiatorfollowed by photopolymerization. The amine functionality may be evenlydistributed throughout the article, or may be present as a surface layerembedded within the article. Of importance to the success of the processis the possession by the monomer of a pendant moiety that is able toreact with the acid H⁺X⁻ in the system. Particularly suitable areprimary, secondary, and tertiary pendant alkylamine groups, which areimmobilized by covalent bonding to one or more polymeric componentswithin the matrix. Specific examples of suitable polyamines arepoly(2-diethylaminoethyl methacrylate) orpoly(2-dimethylaminoethylmethacrylate), their copolymers with each otheror with other amine-functional methacrylates or amine-functionalacrylates, and copolymers of 2-diethylaminoethylmethacrylate or2-dimethylaminoethylmethacrylate with other monomers such as methylmethacrylate or with the monomer of the host polymer.

According to the present invention, the host polymeric article istreated by applying the solvent mixture and acid H⁺X⁻ to at least aportion of its surface for a time and at temperature sufficient tofacilitate at least some infusion of the solvents and acid into thearticle to obtain a treated surface layer, or by immersing the hostpolymeric article in the acid solution for said time. For treatingarticles made of thermoplastic polyurethane, the temperature of thesolvent mixture is about 20° C. to 80° C., most preferably in the rangeof 25° C. to 65° C., and the application time is typically less than onehour, most preferably in the range of 0.1 to 20 minutes. The surface ofthe article is subsequently rinsed with water and dried by treatment inan oven or by passing air over its surface, or by mechanical means.

In one embodiment of the present invention, an article, preferably ofpolyurethane composition and containing a functional polyaminecomponent, is immersed in the acid solution. The solvent mixture at atemperature less than the boiling temperature of the monomer, less thanthe melting temperature of the host polymer, and preferably 25 to 65° C.is applied to the article to be treated. The suitable temperaturedepends on the composition of the article to be treated and may bedetermined by routine or combinatorial testing. In accordance with thisembodiment of the invention, the immersed article is withdrawn afteronly a few minutes to provide a treated article. The length of time thearticle remains immersed in the bath and the process conditions dependupon the desired degree and depth of infusion of H⁺X⁻ into the surfacelayer. Higher temperatures will increase the rate of infusion and depthof penetration. However, care must be taken not to adversely affect thesurface properties of transparent articles used in optical applicationsor to exceed the heat distortion temperature and thus thermally deformthe article.

The application of the solvent mixture to the surface of the article maybe by immersing, spraying, or flow-coating to obtain an articlecontaining the acid solution in the surface layer (treated article).“Spraying” in the present context means applying the solvent solution tothe article in the form of droplets, fog or mist. The term flow-coatingas used herein means applying the solvent solution to the article in theform of a continuous liquid film.

The solvent mixture in the immersion step contains the acid H⁺X⁻, water,a carrier, and an optional leveling agent. The water content of thesolvent mixture is a positive amount up to 80 percent relative to itsweight (pbw), preferably 60 to 75 pbw, more preferably 60 to 70 pbw. Thecarrier is present in the mixture at a positive amount of up to 30 pbw,preferably 15 to 25 pbw, the content of the optional leveling agent isup to 15 pbw, preferably 5 to 15 pbw. The molar concentration of H⁺X⁻ inthe mixture is preferably 0.01 to 5.0 M, more preferably 0.1 to 0.5 M.

According to the present invention, the article is treated by applyingthe solvent mixture to at least a portion of its surface for a time andat temperature sufficient to facilitate at least some infusion of H⁺X⁻into the article to obtain a treated surface layer by converting thepolyamine to a polyamine hydrohalide, an ion-conducting polymer. Fortreating articles made of thermoplastic polyurethane, the temperature ofthe solvent mixture is preferably 25 to 95° C., more preferably in therange of 25 to 65° C. and the application time is preferably less thanone hour, more preferably in the range of 0.1 to 20 minutes. Acceleratedinfusion of H⁺X⁻ may be attained by higher concentration, and/ortemperature and/or time of contact of the solvent mixture with thesurface of the article to be treated. In one embodiment, the preferredconcentration of H⁺X⁻ in the bath is 0.2 M, but there is considerablelatitude in this regard.

The carrier suitable in the context of the invention conformsstructurally toR₁-[—O—(CH₂)_(n)]_(m)OR₂where R₁ and R₂ independently denote a radical selected from linear andbranched C₁₋₁₈ alkyl, benzyl, benzoyl, phenyl and H, n is 2 or 3, and mis 1-35, preferably 1-12, most preferably 1. Aromatic versions of R₁ andR₂ may, independently one from the other, be substituted in the aromaticring by alkyl and or halogen. Most preferably R₁ denotes butyl and R₂denotes H.

The optional leveling agent (in an amount of 0 to 15 pbw, preferably 5to 15 pbw, most preferably 10 to 15 pbw) is an ionic and/or non ionicsubstance promoting even distribution of the precursor over the surfaceof the article. Suitable anionic leveling agents include amine salts oralkali salts of carboxylic, sulfamic or phosphoric acids, for examplesodium lauryl sulfate, ammonium lauryl sulfate, lignosulfonic acidsalts, ethylene diamine tetra acetic acid (EDTA) sodium salts and acidsalts of amines such as laurylamine hydrochloride orpoly(oxy-1,2-ethanediyl), alpha-sulfo-omega-hydroxy ether with phenol1-(methylphenyl)ethyl derivative ammonium salts; or amphoteric, that is,compounds bearing both anionic and cationic groups, for example laurylsulfobetaine; dihydroxy ethylalkyl betaine; amido betaine based oncoconut acids; disodium N-lauryl amino propionate; or the sodium saltsof dicarboxylic acid coconut derivatives. Suitable non-ionic levelingagents include ethoxylated or propoxylated alkyl or aryl phenoliccompounds such as octylphenoxypolyethyleneoxyethanol orpoly(oxy-1,2-ethanediyl),alpha-phenyl-omega-hydroxy, styrenated, polyolsand diols. Suitable diols include the optionally halogen-substituted,linear or branched C₂₋₂₀ aliphatic dials, poly(C₂₋₄ alkylene glycol),C₅₋₈-cycloaliphatic diols, monocyclic aromatic dials and aromaticdihydroxy compounds. A particularly preferred leveling agent isdiethylene glycol.

Leveling agents, such as disclosed in “Lens Prep II”, a commercialproduct of Brain Power International and LEVEGAL DLP a product of BayerMaterialScience LLC (a pre-formulated mixture) are also useful in thepractice of the present invention.

In one embodiment of the inventive process, the acid solution iscontained in one compartment and the article to be treated is positionedin another compartment of the same vessel or in a different vessel. Thesolution is pumped through suitable dispensers, such as atomizingnozzles or manifolds positioned in the vessel containing the article andinert gas, and is applied to the article in a manner calculated toexpose a predetermined area of the article to the solution.

In a variation of this embodiment, the first compartment of the vesselis sized to contain a large article (e.g. sheet) and is equipped with aplurality of nozzles or dispensers positioned so as to enable contactbetween the solution and the article at a sufficient temperature and fora time calculated to infuse the reactive monomer solution to thearticle. These dispensers may be a series of atomizing nozzles creatinga fine mist that covers the surface of the article to be treated, oralternatively, a manifold directing the flow of the reactive monomermixture over the surface of the article. One advantage of thisembodiment of the inventive process over immersion in the solution isthe great reduction, often by a factor of 10, of the quantity of thesolution needed to treat large articles. The limited quantity ofsolution needed makes it possible to also reduce the size of theancillary equipment, such as pumps and heaters.

In addition, the use of nozzles, or alternatively a manifold, directsthe heated monomer mixture directly onto the surface of the article.Hence, the ability to supply fresh solution to the surface of thearticle does not require strong agitation of the solution which isnecessary to achieve uniformity of the treatment in the embodiment whereimmersion is the mode of applying the solution. Note, in the practice ofthis embodiment of the inventive process, the article to be treated isat no time immersed in the heated solvent mixture. Excess solution thatmay drip from the article is collected at the bottom of the firstcompartment containing the article being treated and is transferred backto the second compartment where the solution is brought back to thestarting temperature and recycled. The recycling process is continueduntil the article is infused with the desired level of acid solution.This process may also be designed so that after the article has beentreated, the equipment (e.g., atomizing nozzles) is used to deliver ahigh pressure liquid spray or gas jet to remove excess acid from thetreated article's surface.

The polymeric material may include one or more additives known in theart for their function in the context of these materials. Such additivesinclude, but are not limited to, mold release agents, fillers,reinforcing agents (in the form of fibers or flakes, most notably, metalflakes, such as, aluminum flakes and/or glass) flame retardant agents,light-diffusing agents pigments and opacifying agents, such as, titaniumdioxide and the like, drip suppressants such as polytetrafluoroethylene,impact modifiers, UV-stabilizers, hydrolytic stabilizers and thermalstabilizers.

Articles may be molded by any methods including compression molding,injection molding, rotational molding, extrusion, injection andextrusion blow molding, fiber spinning, and casting; the method ofmolding is not critical to the practice of the inventive process. Thearticles may be any of large variety of items including such as areuseful in the optical, electronics, automotive, entertainment, sportinggoods, and medical sectors. Of particular emphasis are thoseapplications wherein electrostatic dissipation properties are necessaryor beneficial, such as in electronics or engine technology.

The molded articles may be any of a variety of useful items and includetubing for medical, automotive, or other applications, rubber sportinggoods articles, computer keyboards, cellular phones, packaging andcontainers of all types, including ones for industrial components,residential and commercial lighting fixtures and components sheets usedin building and construction, small appliances and their components,optical and sun-wear lenses, biosensors, aircraft components, floor andfurniture coverings, explosive detectors as well as functional filmsincluding such films that are intended for use in film insert moldingand electronics.

EXAMPLES

The present invention is further illustrated, but is not to be limited,by the following examples. All quantities given in “parts” and“percents” are understood to be by weight, unless otherwise indicated.

An exemplary set of experimental data was created using samples of TEXINDP7-1199, a thermoplastic polyurethane elastomer produced by BayerMaterialScience. Injection molded plaques (thickness 3.3 mm) were usedas received from the supplier. The material was impregnated with aninterpenetrating network of poly(2-diethylaminoethylmethacrylate). Thepolymer was soaked in a mixture of (99 pbw2-diethylaminoethylmethacrylate and 1 pbw2,2-dimethoxy-1,2-di(phenyl)ethanone) for 20 minutes at 22° C., thenexposed to a 100 W, ultraviolet light source (365 nm peak wavelength)for five minutes under flowing nitrogen atmosphere. The process createda semi-interpenetrating network of poly(2-diethylaminoethylmethacrylate)in a shallow surface layer of the host polymer.

The overall mass fraction of the semi-interpenetrating network was 0.05.The material was immersed in a 0.2 M HCl solution in the infusionsolvent (70% water, 20% butyl cellosolve, and 10% diethylene glycol, byvolume) for 60 min at 65° C. Following the acid infusion, samples wereair dried for at least 24 hours at 22° C. The surface resistivity of thetreated material was determined to be about 10⁹Ω/□, falling within theelectrostatic dissipation range, whereas the surface resistivity of theunmodified DP7-1199 TPU was determined to be on the order of 10¹⁴Ω/□,falling within the electrically insulating range. Resistivity wasmeasured with a Keithley 6517b high-resistance electrometer and 8009resistivity test fixture.

The foregoing examples of the present invention are offered for thepurpose of illustration and not limitation. It will be apparent to thoseskilled in the art that the embodiments described herein may be modifiedor revised in various ways without departing from the spirit and scopeof the invention. The scope of the invention is to be measured by theappended claims.

What is claimed is:
 1. A process comprising contacting at least a partof a surface of a polymeric article with a solvent mixture for a timeand at a temperature sufficient to infuse at least a portion of thesolvent mixture into the article, the solvent mixture containing; (a)water, (b) a carrier conforming toR1-[O—(CH2)n]mOR2 wherein R1 and R2 independently denote a radicalselected from the group consisting of linear and branched C1-18 alkyl,benzyl, benzoyl, phenyl and H, wherein n is 2 or 3, and m is 1-35, and(c) an acid H+X—, wherein X— represents a halide anion selected from thegroup consisting of F—, Cl—, Br—, or I—, optionally, (d) a surfaceleveling agent, wherein the polymeric article comprises a host polymerand an immobilized amine functional species wherein a monomer of apendant moiety of the amine functional species is capable of reactingwith the acid H+X−, and wherein the resulting article has a treatedsurface layer containing a polyamine hydrohalide and a surfaceresistivity between about 1×105Ω/□ and about 1×1012Ω/□.
 2. The processaccording to claim 1, wherein the polymeric article contains at leastone component selected from the group consisting of polyurethane,polyester, polyamide, polystyrene, polyetherimide,polymethylmethacrylate and acrylonitrile butadiene styrene.
 3. Theprocess according to claim 1, wherein the amine functional species is anamine-functional co-monomer.
 4. The process according to claim 1,wherein the acid is a member selected from the group consisting of HF,HCl, HBr, or Hl.
 5. The process according to claim 1, wherein thecontacting is one selected from the group consisting of immersion,spraying and flow coating.
 6. A process for producing an electrostaticdischarge material comprising, contacting at least a part of a surfaceof a polymeric article with a solvent mixture for a time and at atemperature sufficient to infuse at least a portion of the solventmixture into the article, the solvent mixture containing; (a) water, (b)a carrier conforming toR1-[O—(CH2)n]mOR2 wherein R1 and R2 independently denote a radicalselected from the group consisting of linear and branched C1-18 alkyl,benzyl, benzoyl, phenyl and H, wherein n is 2 or 3, and m is 1-35, and(c) an acid H+X−, wherein X— represents a halide anion selected from thegroup consisting of F—, Cl—, Br—, or I—, optionally, (d) a surfaceleveling agent, wherein the polymeric article comprises a host polymerand an immobilized amine functional species wherein a monomer of apendant moiety of the amine functional species is capable of reactingwith the acid H+X−, and wherein the resulting electrostatic dischargematerial has a treated surface layer containing a polyamine hydrohalideand a surface resistivity between about 1×105Ω/□ and about 1×1012Ω/□. 7.The process according to claim 6, wherein the polymeric article containsat least one component selected from the group consisting ofpolyurethane, polyester, polyamide, polystyrene, polyetherimide,polymethylmethacrylate and acrylonitrile butadiene styrene.
 8. Theprocess according to claim 6, wherein the amine functional species is anamine-functional co-monomer.
 9. The process according to claim 6,wherein the acid is a member selected from the group consisting of HF,HCl, HBr, or Hl.
 10. The process according to claim 6, wherein thecontacting is one selected from the group consisting of immersion,spraying and flow coating.